Waterproofing-coating composition for concrete, &amp;c.



UNITED STATES PATENT OFFICE. f

GABLE'ION ELLIS, or mon'ronam, NEW annsnmassmnon To ELLIS-FOSTER oomrm,

\ A oonromrrono'r NEW JERSEY,

warnnrnoorme-coarme oomrosrrron FOR concnn'rn, 6w;

No Drawing.

To all whom it may concern:

Be it known that I, CARLETON ELLIS, a citizen of the United States,and aresident of Montclair, in the county of Essex and w State of New Jersey, have invented certain new and useful Improvements in Waterproofing-Coating Com ositions for Concrete, &c., of which the fol owing is a specification.

This invention relates to a composition of matter adapted for use as a vehicle for painting concrete and cement structures of diverssorts and relates particularly to a composition containing rubber resin, all as more fully hereinafter described and claimed.

Concrete made from Portland cement is ordinarily rather porous and lacking in waterproof qualities; also it has a grayish brown tint as usually prepared which, for certain purposes is not desired. The cement used in the concrete containsa considerable amount of alkali in theform of free lime, or lime in loose combination; also potash or soda in basic form. In addition, bodies of a more or less water soluble nature are present and these comp ounds, under the action of moisture tend to migrate from the interior of. the concrete mass and appear on the surface thereof as a white etllorescence known by the artisan as saltpeter 0r lime stains. These are very unsightly and often greatly injure the appearance of buildings, such as dwelling houses constructed of solid or monolithic concrete and stucco. Moreover, the surface of concrete often undergoes a slight disintegration, known as checking, which renders the surface unsightly, so for these and other reasons, concrete surfaces frequently need to be painted.

The basis of ordinary paint, linseed oil, is not adapted for use in the painting of concrete. Linseed oil, being a readily saponifiable oil, is affected by-the alkalis of the ce- 45 ment and perishes rather rapidly. With the idea of overcoming these difficulties, proposals have been made to treat the surface of the concrete, prior to painting, withv an acid, or neutralizing wash, such as aque- 50 ous solutions of hydrochloric and sulfuric acids, zinc sulfate, ammonium carbonate Specification of Letters Patent. Application filed February is, 1911.

-. Patented Aug. 1, 1911.

sxnarm. ceases. x and the ike. In addition to the time required to apply such awash, the work has to be delayed in order to permit the water to dry out before the paint is applied and the surface-of the cement, because of. such drastic acid treatment, is oftentimes more or less disintegrated, the bonding of the cement is in a measure destroyed, especially at the surface, leading to scaling and checkmg. Th1 s action is enhanced by the actionof frost 1n winter and may lead to a very great deterioration of the painted surface. Then too, there is always danger that alkalis from the interior of the cement mass may find their way to the surface of the mass and affect the paint coating by saponifying action; for the neutralizing action ofthe acid wash is only superficial at best,

lea ing the interior of the cement with its full quota of unneutralized alkali. For

this and other reasons linseed oil has not but these also are saponifiable to a very considerable degree and are open in a large measure to the same objections noted in the case of linseed oil. Y

My invention hasto do with paint vehicles which essentially are substantially free from binding materials. affected by the alkalis of cement, and comprises the useof resins, or resinous materials extracted from rubber gums and in particular the rubber gum known as jelutong.

Different qualitiw of' jelutong are known in the trade, according to the source from which they are derived, as Palembang, (Sumatra) Pontianak, (Borneo), Sarawak, and the like. Commercial jelutong is obtained by coagulating the latex derived from the jelutong tree. Commercial jelua "tong contains roughly about 70% water, and 30% solid material, the latter consisting of about one third rubber and two thirds "r'sin, so that for about each pound of rubberrecovered, about two pounds of resin are obtained. The resin has found but few uses, and-.hasconstituted a waste, or by-product of considerable magnitude.

The process of deresination as now practiced by the aid of solvents, leaves the resin in the form of a mass of white particles, or friable lumps, usually containing some moisture and the method of treatment for rendering this resin suitable as a basis for concrete paint vehicles, of oils, will shortly be de scribed.

Jelutong resin, as for example, Pontianak, is practically unsaponifiable, as I have indicated in U. S.- Letters Patent No. 900,687 of Oct. 6th, 1908. While the resin after melting, is similar in appearance to ordinary colophonium, it is widely. different chem1- cally and because of this, unfit for the many uses to which colophonium is adapted.

Thus, because of its unsaponifiability, Pontianak rubber resin cannot be used, as is rosin, in the manufacture of soaps, etc.

Chute has called attention to the difficulty of utilizing Pontianak rubber resin, (I wZz'a Rubber W orld, July 1st, 1909) and has given some data as to the properties of this resin,

His data as to the solutions of this resin coincide to a considerable extent with my own observations, except that no mention has been made by Chute of the instability of many of the solutions of resin. When first prepared, clear solutions are readily obtained, as, for example, by melting one part of Pontianak rubber resin and thinning with two parts of petroleum naphtha. Such a clear solution is however, supersaturated and on keeping for a few weeks or months oreven longer, separation of the less soluble portion occurs spontaneously and the former clear solution becomes largely a grayish paste, or solid mass. Most common solvents act in this way as the following tabulation indicates: For example, a clear liquid mixture made from equal parts of Pontianak resin and pine oil, on standing for a considerable period becomes solid; with one part resin and two parts pine oil, it is about one half solid; with one part resin and one part each of pine oil and solvent naphtha, nearly solid. Nearly solid roducts are produced on standing by mixing two parts of Pontianak resin with one part each of pine oil and heavy benzin,'two partsof the resin to one part pine oil and two parts of heavy benzin, also two arts resin to two parts each of these so vents 've like results. Light benzin, (varnish ma ers benzin) with pine oil in varying proportions, acts in the same way. Equal parts of the resin and spirits of turpentine solidify as 0 mixtures composed of three and four parts of turpenmoderate concentration.

eeavoe However, two parts of the resin" with one and one-half, two and two and one-half parts of ordinary crude solvent naphtha solidify completely, three parts of solvent naphtha is nearly solid, while three and onehalf and four parts of the solvent yield three-quarters solid and one-quarter liquid.

Two parts resin to three parts varnish.

have a similar solidifying action. Mixtures I of benzol and benzin with the resin are somewhat unstable. Russian turpentine has better solvent properties than ordinary spirits of turpentine but in the course of time, solidification sets in with solutions of Guayule resin is permanently soluble in the solutions mentioned and seems to exert some influence in -maintaining the Pontianak resin in solution.

The foregoing mixtures, which segregate solid material do not dry properly, especially when exposed in moderately thick films. If a very thin film is allowed to dry,

'say on a glass plate it may become hard,

HESS.

There is great uncertainty respecting the permanency of such solutions in storage.

The solidification may occur in a few days or the solutions may retain their mobility and clarity for a long time to finally coagulate and become worthless as finish coating material. The various factors which enter into the phenomena of spontaneous coagulation have not as yet been fully determined by me and I content myself for the present simply with calling attention to these ob"- servations.

In the preparation of finish coatings, such as paint oils, varnishes and the like, concentrated solutions of resin are often required. For example, making rosin varnish known as the gloss oil type, five or six parts of ordinary rosin are used to four or five parts of benzin. With Pontianak rubber resin, ordinarily such. concentrations would be impossible to secure.

In the manufacture of varnish from hard resins, it is quite customary to heat such resins to a temperature of 500 to 600 degrees F. in order to render them more suitable posed that a temperature of 400 degrees could not be exceeded, owing to the forma tion of acetic acids and. other supposedly injurious bodies. I have found-however, that this is not the case, but that it is entirely feasible to heat Pontianak resin to a temperature of even 600 degrees, or higher, thereby producing a solution which is readily soluble in ordinary volatile thinners, customarily used in varnish manufacture. In order to obtain such a high degree of solubility, I find that by heating the resin for about an hour at about 600-620 degrees F. gives a loss in weight of about'20% and suffices to render'the product readily soluble in thinning mediums, such as benzol benzin and the like. In fact, by such treatment itbecomes possible to make a solution in say benzol for example, of just as high a concentration as that obtained in ordinary rosin gloss oil. This is a very important consideration, because a concentrated solution is ordinarily required in coating materials and the dilute mixtures obtained by the solutions of the raw Pontianak resin in volatile thinners do not give for many purposes the requisite degree of-concentration. Another important advantage is that such concentrated solutions derived from the employment of resin heated to 600 degrees or thereabout as above indicated, is the very noticeable mobility of these solutions. Ordinary gloss oil, containing 50% or 60% of rosin is usually relatively thick and rather viscous, so that when Worked out under the brush, considerable drag is experienced and brush marks often appear. In the present case, it is possible to secure relatively thin solutions of unusually high concentration, which work with very great freedom under the brush. While ordinary gloss oil is destroyed in a short time by the action of the sun and rain, the Pontianak resin, treated in this manner, shows an unusual degree of resistance to atmospheric influence.

Solutions of the resins, suitable as paint vehicles may be made in the following way :125 lbs. of Pontianak resin is heated for one hour at about 600 degrees F., giving a loss of about 25 lbs. The molten resin is-cooled toabout 300 degrees F. and thinned with 90 or 100 lbs. of benzol. Or a mix: ture of equal parts of benzol and benzin may be used for thinning, likewise other common solvents, such as turpentine, wood turpentine, texene, solvent naphtha, toluol and the like may be employed, it'being possible even with solvents, such as texene, which is not as powerful in its solvent properties as solvent naphtha or benzol, for exconstituents, or

its compounds having bleaching .changes which take place are,

ample, to. secure solutions of fairly high concentration. The solutions made in this way may, if desired, be incorporated with drying oils and driers, including, fish, linseed,

china wood, corn, and soya bean oils. Alsomanganese and lead oleate andlinoleate and guayule resin may be incorporated, the latter especially if a very high gloss is desired.

Instead of heating at 600 degrees for one hour, the resin may be heated ata somewhat lower temperature for a longer period, as for example, at 550 degrees F. for two hours or 500 degrees for four hours. If

however, the resin is not heated above400 degrees F. the desired degree of solubility not secured, nor the desirable properties of mobility and free operation under the brush. The heat treatment may be somewhat shortened by blowing air through the resin, or even by treatment with superheatedsteam, or inert gases, which tend to accelerate the removal of the undesirable and insoluble causes changes in these which brings about the desired properties above mentioned. y

When run at a temperature of 600 degrees or higher, the resulting solution is somewhat dark in color, and this may be bleached, if

desired, by filtration through fullers earth or bone black, or by treatment with chemical bleaching agents, such as chlorin and properties, sodium peroxid, ozone and the like.

Owing to the fact that at temperatures above 400 degrees deep seated changes take place in the resin, rendering it a compound seemingly having almost entirely different properties, itwouldbe expected that organic acids would develop which would give the composition a marked saponification equivalent. I find however, that this is not the case, although if the material is heated at 500 degrees or 600 degrees F. with hydrated lime for a long period, a small quantity of the lime is taken up by the resin apparently, resulting in a product which is slightly harder than the unlimed resin. The however, so far as can be judged, those of polymerization and depolymerization, so that the very desirable quality of unsaponifiability may be caused to remain substantially unchanged.

The treatment of the resin at perature may take place if desired at reduced atmospheric pressure, the temperature and length or heat treatment under such circumstances, de ending upon the amount of reduction 0 atmospheric pres sure prevailing.

The oil secured for example by heating the resin at 600 degrees F. for one hour under ordinary atmospheric pressure through. thinning with a mixture of equal parts of benzol and benzin after the heat high tem- Such a product mixed with say soya beanoil in the proportion oftwo parts of the resin solution to one part of the oil andthe addition of a small amount of Japan drier,

yields a very useful paint oil, and as stated,

other, drying oils may be used if desired, wood oil however, being open to the oby'ection that it tends to oxidize more or in such solutions, when standing in containers, especially partly filled barrels, etc., and gelatinization brought about by such changes, makes it not as useful as certain of the other oils mentioned, which are free. from this objection, as for example linseed oil and fish oil. I

In applying this composition to concrete, for which purpose it serves as-an excellent paint on account of its substantial unsaponifiability, I prefer to not introduce any drying oil, but use the simple solution of run resin. .There is no objection however,

1 to the employment of pigment ground in a drying oil, as the small percentage of saponifiable oil introduced in this manner is not detrimental, because when applied to the concrete this oil is so largely surrounded and embedded, as it were, in unsaponifiable material, that the alkalis of cement do not affect it in the usual way. When a flatting efiect is desired on the concrete work for example, the addition to the oil of the aluminum soap of Chinese wood oil, containing aluminum eleomargarate, may be used to advantage in an amount of 5% or 10%, and if desired, 2% or 3%, for example of ceresin wax may be introduced.

The resin run at 600 degrees, F. more or less, as above described, may be mixed with a quantity of the raw resin and a solution made of this which affords an excellent waterproofing medium for porous stone, brick and concrete, and is usually of lighter color than the solutions run of resin alone. Furthermore the presence of the run resin seems to lend stability to the raw resin in solution rendering the latter less liable to separate when exposed to low temperatures. For such waterproofing applications, a solution of raw resin, one part in two parts of benzol may be mixed with a solution of equal parts of the run benzol and resin.' Three volumes of the raw resin solution to one volume of the raw resin solution is a very satisfactory proportion. Or the composition may be made by heating 125 lbs. jelutong resin for one hour at 610 degrees F., adding 200 lbs. more resin and when this'is melted, 75 gal. to 100 gal. of benzol, or a mixture of benzol and benzin are introduced.

I do not lay claim in this application to BSS the rocessjof using such unsa onifia'ble oil 1 rial No. 588,549. Nor do and guayule resins, set forth in my co-pend ing application, Serial No. 552,178 except as same may relate to the herein described product.

Reference is also made to Serial No. 628,577 as regards divisional matter derived from Serial No. 588,549, which matter is not claimed herein.

Havin described my invention, to'the details .0 which I do not wish to be limited, what I claim is- '1. A composition of matter comprising rubber resin heated to at least 500 degrees F.

2. A composition of matter comprising jelutong rubber resin, heated above 500 degrees F.

3. A composition of matter comprising Pontianak rubber resin heated above 500 degrees F.

4. A composition of matter comprising Pontianak rubber resin heated between 500 degrees and 650 degrees, F.

lay'claim herein to the various applications of Pontianak 5. A composition of matter comprising Pontianak rubber resin heated between 500 degrees and 600- degrees F. with a loss of about 20% in weight.

6. A composition of matter comprising Pontianak rubber resin heated between 500 degrees and 650 degrees F. for about one hour, in a solution of a volatile hydrocarbon solvent.

7. A paint oil comprising the solution in a volatile solvent of jelutong rubber resin run at from 500 degrees to 650 degrees F.

8. A paint oil consisting of heat treated Pontianak rubber resin in a volatile hydrocarbon solvent, the concentration of the rubber resin exceeding 25%.

9. A paint oil comprising a solution of heat treated Pontianak rubber resin in a mixture of about equal parts of benzol and benzin, the concentration of said resin being approximately 50%.

10. A paint oil for priming and coating concrete, comprising heat-changed jelutong rubber resin in a suitable solvent.

11. A paint oil for priming and coating concrete comprising heat-changed jelutong rubber resin in a substantially volatile hydrocarbon solvent.

12. A paint oil for priming and coating concrete comprising heat-changed substantially unsaponifiable resin and a volatile thinner.

13. A paint oil for riming and coating concrete comprising eat treated rubber resin and untreated rubber resinin solution in a volatile thinner.

14. A paint oil for priming and coating concrete containing heat treated rubber Signed at Montclair in thecounty oi Esresin and untreated rubber resin in solution sex and State of New Jersey this 10th day I ima volatile hydrocarbon thinner. of February A. D. 1911.

15. A paint oil for priming and coating CARLETON ELLIS. 5 concrete comprising jelutong rubber resin, Witnesses:

substantially freed by heat treatment from NATHANIEL L. FOSTER,

rubber-like impurities. B, M. ELLIS. 

